Rogers won their only previous encounter 6-1 6-1 in New Haven in 2016 and was also a French Open quarter-finalist a year ago, while 13th seed Mladenovic has never progressed past the third round in eight visits to Roland Garros prior to this year.
Opening proceedings on Court Philippe Chatrier will be defending champion Garbine Muguruza, the fourth seed playing Kazakh 27th seed Yulia Putintseva, with a possible mouth-watering fourth-round clash against Mladenovic looming.
Nine-time champion Rafa Nadal and title holder Novak Djokovic are also in third round action, facing off against Georgian Nikoloz Basilashvili and Argentine Diego Schwartzmann respectively.
Austrian sixth seed Dominic Thiem, one of the rising stars of the sport, takes on American Steve Johnson on Court One.
Temperatures in Paris are forecast to be sweltering again but there is a risk of hailstorms in the afternoon, which could disrupt a packed schedule.
(Reporting by Julien Pretot; Editing by John O'Brien)
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